JP2009275178A - Modified conjugated diene-based polymer composition and vulcanized rubber composition using the same - Google Patents
Modified conjugated diene-based polymer composition and vulcanized rubber composition using the same Download PDFInfo
- Publication number
- JP2009275178A JP2009275178A JP2008129920A JP2008129920A JP2009275178A JP 2009275178 A JP2009275178 A JP 2009275178A JP 2008129920 A JP2008129920 A JP 2008129920A JP 2008129920 A JP2008129920 A JP 2008129920A JP 2009275178 A JP2009275178 A JP 2009275178A
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- diene polymer
- mass
- modified conjugated
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 120
- 150000001993 dienes Chemical class 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 7
- -1 glycidyl amino group Chemical group 0.000 claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 239000000539 dimer Substances 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims description 34
- 229920001194 natural rubber Polymers 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 9
- 229920003052 natural elastomer Polymers 0.000 claims description 9
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 7
- 239000012763 reinforcing filler Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 abstract description 22
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 150000003384 small molecules Chemical class 0.000 abstract description 10
- 238000005299 abrasion Methods 0.000 abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 68
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 56
- 239000000523 sample Substances 0.000 description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
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- CTDOPUVVTOMREJ-UHFFFAOYSA-N 1,3-dimethylidenecyclohexane Chemical compound C=C1CCCC(=C)C1 CTDOPUVVTOMREJ-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
Description
本発明は、変性共役ジエン系重合体組成物に関する。 The present invention relates to a modified conjugated diene polymer composition.
近年、省資源化や環境問題への関心の高まりから、自動車の低燃費化への要望が高まってきている。このような要求に対応するため、タイヤに関しても燃費性能の良い材料、即ち転がり抵抗の小さい材料の開発が求められている。また同時に、走行時の操縦安定性は必須の特性である。操縦安定性が良好であるためには、ウェットスキッド抵抗が大きい材料が好ましい。従って、自動車タイヤ用材料は、転がり抵抗とウェットスキッド抵抗とのバランスに優れ、更には耐摩耗性や剛性といった物理的強度にも優れていることが要求される。 In recent years, demands for reducing fuel consumption of automobiles have increased due to increased interest in resource saving and environmental problems. In order to meet such demands, the development of materials with good fuel efficiency, that is, materials with low rolling resistance, is also required for tires. At the same time, steering stability during driving is an essential characteristic. In order to have good steering stability, a material having a large wet skid resistance is preferable. Accordingly, automobile tire materials are required to have an excellent balance between rolling resistance and wet skid resistance, as well as excellent physical strength such as wear resistance and rigidity.
タイヤの転がり抵抗を低減するためには、一般的に、発熱性の低いゴム材料が用いられる。発熱性の低いゴム材料としては、例えば、天然ゴム、ポリイソプレン、ポリブタジエン等が知られているが、これらは、上記ウェットスキッド抵抗に劣るという問題を有している。 In order to reduce the rolling resistance of the tire, a rubber material having low heat generation is generally used. For example, natural rubber, polyisoprene, polybutadiene and the like are known as rubber materials having low exothermic properties, but these have a problem that they are inferior in the wet skid resistance.
ウェットスキッド抵抗を損なうことなく転がり抵抗を低減する方法として、従来、炭化水素溶媒中で有機リチウム開始剤により重合された種々の構造のスチレン−ブタジエン共重合体の重合体末端に変性基を導入する方法が提案されている。 As a method for reducing rolling resistance without impairing wet skid resistance, conventionally, a modified group is introduced into a polymer end of a styrene-butadiene copolymer having various structures polymerized with an organolithium initiator in a hydrocarbon solvent. A method has been proposed.
また、耐摩耗性を高めるためには、耐摩耗性に優れた材料であるポリブタジエン等を配合する方法が知られている。剛性を高めるためには、充填する補強剤組成を改良する技術が知られているが、ゴム材料の改良としては、高分子量化する以外に効果的な方法がなかった。 In order to improve wear resistance, a method of blending polybutadiene or the like, which is a material excellent in wear resistance, is known. In order to increase the rigidity, a technique for improving the composition of the reinforcing agent to be filled is known, but there is no effective method for improving the rubber material other than increasing the molecular weight.
例えば、下記特許文献１〜４には、重合体の活性末端と分子中にエポキシ基および３級アミノ基を有する低分子化合物を反応させることで、転がり抵抗とウェットスキッド抵抗のバランスが改善されたゴム組成物が得られることが開示されている。 For example, in Patent Documents 1 to 4 below, the balance between rolling resistance and wet skid resistance is improved by reacting a low molecular compound having an epoxy group and a tertiary amino group in the molecule with the active terminal of the polymer. It is disclosed that a rubber composition is obtained.
しかしながら、これらの重合体を用いたゴム組成物では転がり抵抗とウェットスキッド抵抗のバランスは改良されるが、剛性や耐摩耗性はまだ充分ではなかった。
そこで本発明においては、加硫処理を施して加硫ゴムとしたときに、転がり抵抗とウェットスキッド抵抗のバランスに優れ、剛性や耐摩耗性といった機械的特性にも優れたゴム組成物を提供することを目的とする。
However, although the rubber composition using these polymers improves the balance between rolling resistance and wet skid resistance, rigidity and wear resistance are still insufficient.
Therefore, in the present invention, when a vulcanized rubber is obtained by performing a vulcanization treatment, a rubber composition having an excellent balance between rolling resistance and wet skid resistance and excellent mechanical properties such as rigidity and wear resistance is provided. For the purpose.
本発明者等は、前記課題を解決するために鋭意検討した結果、特定の官能基を末端に有する高ビニル変性共役ジエン系重合体を配合することによって、転がり抵抗とウェットスキッド抵抗のバランスが改良されるだけでなく、さらに剛性と耐摩耗性に優れた変性共役ジエン系重合体組成物を見出し、本発明をなすに至った。ここで、高ビニル変性共役ジエン系重合体とは、共役ジエン部の１，２−結合または３，４−結合の比率が高い、即ちビニル結合量が多い共役ジエン系重合体のことである。 As a result of intensive studies to solve the above problems, the present inventors have improved the balance between rolling resistance and wet skid resistance by blending a high vinyl-modified conjugated diene polymer having a specific functional group at the end. In addition, the present inventors have found a modified conjugated diene polymer composition that is further excellent in rigidity and wear resistance and has achieved the present invention. Here, the high vinyl-modified conjugated diene polymer is a conjugated diene polymer having a high ratio of 1,2-bonds or 3,4-bonds in the conjugated diene part, that is, a large amount of vinyl bonds.
請求項１の発明においては、下記（Ａ）、（Ｂ）を含有する変性共役ジエン系重合体組成物を提供する。
（Ａ）下記変性共役ジエン系重合体（Ａ−１）と、当該（Ａ−１）とは異なるゴム成分（Ａ−２）とからなる変性共役ジエン系重合体組成物であって、（Ａ−１）と（Ａ−２）との質量比が１０／９０〜９０／１０である変性共役ジエン系重合体組成物。
ここで、（Ａ−１）は、共役ジエン化合物と芳香族ビニル化合物とが重合した共役ジエン系重合体の活性末端が変性剤と結合しているものであり、下記（ａ）〜（ｃ）の条件を満たしている変性共役ジエン系重合体である。
（ａ）前記変性剤が、分子中にグリシジルアミノ基を含む低分子化合物７５〜９５質量 ％と、当該低分子化合物の２量体以上のオリゴマー２５〜５質量％とからなる変 性剤である。
（ｂ）前記共役ジエン系重合体中の、共役ジエン化合物／芳香族ビニル化合物の質量比 が８５／１５〜６５／３５である。
（ｃ）前記共役ジエン系重合体中の共役ジエン部の１，４−結合／１，２−結合または ３，４−結合の比率が、５０／５０〜２５／７５である。
（Ｂ）補強性充填剤（但し、前記（Ａ）１００質量部に対して、１〜２００質量部。）。
The invention of claim 1 provides a modified conjugated diene polymer composition containing the following (A) and (B).
(A) A modified conjugated diene polymer composition comprising the following modified conjugated diene polymer (A-1) and a rubber component (A-2) different from (A-1), -1) and a modified conjugated diene polymer composition having a mass ratio of (A-2) of 10/90 to 90/10.
Here, (A-1) is one in which the active end of a conjugated diene polymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound is bonded to a modifier, and the following (a) to (c) It is a modified conjugated diene polymer that satisfies the above conditions.
(A) The modifier is a modifier composed of 75 to 95% by mass of a low molecular compound containing a glycidylamino group in the molecule and 25 to 5% by mass of an oligomer that is a dimer or higher of the low molecular compound. .
(B) The mass ratio of the conjugated diene compound / the aromatic vinyl compound in the conjugated diene polymer is 85/15 to 65/35.
(C) The ratio of 1,4-bond / 1,2-bond or 3,4-bond of the conjugated diene moiety in the conjugated diene polymer is 50/50 to 25/75.
(B) Reinforcing filler (however, 1 to 200 parts by mass with respect to 100 parts by mass of (A)).
請求項２の発明においては、前記ゴム成分（Ａ−２）が、天然ゴム、ポリイソプレン、及びシス−１，４−ポリブタジエンからなる群から選択される少なくとも１種である請求項１に記載の変性共役ジエン系重合体組成物を提供する。 In the invention of claim 2, the rubber component (A-2) is at least one selected from the group consisting of natural rubber, polyisoprene, and cis-1,4-polybutadiene. A modified conjugated diene polymer composition is provided.
請求項３の発明においては、請求項１又は２に記載の変性共役ジエン系重合体組成物を加硫してなる加硫ゴム組成物を提供する。
The invention of
本発明の変性共役ジエン系重合体組成物は、加硫処理を施して加硫ゴムとした時に、転がり抵抗とウェットスキッド抵抗のバランスに優れ、さらに剛性、耐摩耗性にも優れたゴム組成物を提供することができる。 The modified conjugated diene polymer composition of the present invention is a rubber composition having an excellent balance between rolling resistance and wet skid resistance, and also excellent rigidity and wear resistance when vulcanized to give a vulcanized rubber. Can be provided.
以下、本発明を実施するための最良の形態（以下、本実施の形態）について詳細に説明する。なお、本発明は、本実施の形態に限定されるものではなく、要旨の範囲内で種々変形して実施することができる。 Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. The present invention is not limited to the present embodiment, and can be implemented with various modifications within the scope of the gist.
本実施の形態における変性共役ジエン系重合体組成物のゴム成分は、後述する変性共役ジエン系重合体（Ａ−１）と、当該（Ａ−１）とは異別のゴム成分（Ａ−２）とから構成されている。変性共役ジエン系重合体（Ａ−１）とゴム成分（Ａ−２）との質量比は、１０／９０〜９０／１０である。
変性共役ジエン系重合体（Ａ−１）は、共役ジエン化合物と芳香族ビニル化合物とが重合した共役ジエン系重合体の活性末端が変性剤と結合しているものであり、下記（ａ）〜（ｃ）の条件を満たしているものとする。
（ａ）前記変性剤が、分子中にグリシジルアミノ基を含む低分子化合物７５〜９５質量 ％と、当該低分子化合物の２量体以上のオリゴマー２５〜５質量％とからなる変 性剤である。
（ｂ）前記共役ジエン系重合体中の、共役ジエン化合物／芳香族ビニル化合物の質量比 が８５／１５〜６５／３５である。
（ｃ）前記共役ジエン系重合体中の共役ジエン部の１，４−結合／１，２−結合または ３，４−結合の比率が、５０／５０〜２５／７５である。
The rubber component of the modified conjugated diene polymer composition in the present embodiment is a modified conjugated diene polymer (A-1) described later and a rubber component (A-2) different from (A-1). ). The mass ratio of the modified conjugated diene polymer (A-1) and the rubber component (A-2) is 10/90 to 90/10.
The modified conjugated diene polymer (A-1) is one in which the active terminal of a conjugated diene polymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound is bonded to a modifier. It is assumed that the condition (c) is satisfied.
(A) The modifier is a modifier composed of 75 to 95% by mass of a low molecular compound containing a glycidylamino group in the molecule and 25 to 5% by mass of an oligomer that is a dimer or higher of the low molecular compound. .
(B) The mass ratio of the conjugated diene compound / the aromatic vinyl compound in the conjugated diene polymer is 85/15 to 65/35.
(C) The ratio of 1,4-bond / 1,2-bond or 3,4-bond of the conjugated diene moiety in the conjugated diene polymer is 50/50 to 25/75.
〔変性共役ジエン系重合体（Ａ−１）〕
変性共役ジエン系重合体（Ａ−１）は、一方の末端が重合活性末端である共役ジエン系重合体に変性剤を反応させて得られる。
[Modified Conjugated Diene Polymer (A-1)]
The modified conjugated diene polymer (A-1) is obtained by reacting a modifier with a conjugated diene polymer having one terminal at the polymerization active terminal.
先ず、変性剤について説明する。
変性剤は、分子中にグリシジルアミノ基を含む低分子化合物７５〜９５質量％と、この低分子化合物の２量体以上のオリゴマー２５〜５質量％とからなるものである。なお、前記低分子化合物および前記オリゴマーの含有量は、変性剤全量に対する質量％である。前記オリゴマーは、前記低分子化合物の２量体〜１０量体が好ましい。
前記低分子化合物は、分子量が１０００以下の有機化合物であり、下記一般式（１）の化合物が好適なものとして挙げられる。
First, the modifier is described.
The denaturant is composed of 75 to 95% by mass of a low molecular compound containing a glycidylamino group in the molecule and 25 to 5% by mass of an oligomer of a dimer or higher of the low molecular compound. In addition, content of the said low molecular compound and the said oligomer is the mass% with respect to modifier | denaturant whole quantity. The oligomer is preferably a dimer to a 10-mer of the low-molecular compound.
The low molecular weight compound is an organic compound having a molecular weight of 1000 or less, and a compound represented by the following general formula (1) is preferable.
上記一般式（１）において、Ｒは２価の炭化水素基またはエーテル、エポキシ、ケトン等の酸素を含む極性基、チオエーテル、チオケトン等の硫黄を含む極性基、３級アミノ基、イミノ基等の窒素を含む極性基から選ばれる少なくとも一種の極性基を有する２価の有機基である。２価の炭化水素基としては、飽和または不飽和の直鎖状、分岐状、環状であってもよく、例えば、アルキレン基、アルケニレン基、フェニレン基などを含む。具体的には、例えば、メチレン、エチレン、ブチレン、シクロヘキシレン、１，３−ビス（メチレン）−シクロヘキサン、１，３−ビス（エチレン）−シクロヘキサン、ｏ−フェニレン、ｍ−フェニレン、ｐ−フェニレン、ｍ−キシレン、ｐ−キシレン、ビス（フェニレン）−メタンなどが挙げられる。
この一般式（１）で表される低分子化合物の具体例としては、テトラグリシジル−１,３−ビスアミノメチルシクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、４，４−メチレン−ビス（Ｎ，Ｎ−ジグリシジルアニリン）、１，４−ビス（Ｎ，Ｎ−ジグリシジルアミノ）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル-ｐ-フェニレンジアミン、４，４’−ビス（ジグリシジルアミノ）ベンゾフェノン、４−（４−グリシジルピペラジニル）−（Ｎ，Ｎ−ジグリシジル）アニリン、２−[２−（Ｎ，Ｎ−ジグリシジルアミノ）エチル]−１−グリシジルピロリジン等が挙げられる。
特に、テトラグリシジル−１,３−ビスアミノメチルシクロヘキサンが好ましい。
In the above general formula (1), R is a divalent hydrocarbon group or a polar group containing oxygen such as ether, epoxy or ketone, a polar group containing sulfur such as thioether or thioketone, a tertiary amino group, or an imino group. It is a divalent organic group having at least one polar group selected from polar groups containing nitrogen. The divalent hydrocarbon group may be a saturated or unsaturated linear, branched, or cyclic group, and includes, for example, an alkylene group, an alkenylene group, a phenylene group, and the like. Specifically, for example, methylene, ethylene, butylene, cyclohexylene, 1,3-bis (methylene) -cyclohexane, 1,3-bis (ethylene) -cyclohexane, o-phenylene, m-phenylene, p-phenylene, m-xylene, p-xylene, bis (phenylene) -methane and the like can be mentioned.
Specific examples of the low molecular weight compound represented by the general formula (1) include tetraglycidyl-1,3-bisaminomethylcyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 4 , 4-methylene-bis (N, N-diglycidylaniline), 1,4-bis (N, N-diglycidylamino) cyclohexane, N, N, N ′, N′-tetraglycidyl-p-phenylenediamine, 4,4′-bis (diglycidylamino) benzophenone, 4- (4-glycidylpiperazinyl)-(N, N-diglycidyl) aniline, 2- [2- (N, N-diglycidylamino) ethyl]- 1-glycidylpyrrolidine and the like can be mentioned.
In particular, tetraglycidyl-1,3-bisaminomethylcyclohexane is preferable.
前記オリゴマー成分としては、下記一般式（２）で表される２量体や、一般式（３）で表される３量体が好適な例として挙げられる。 Preferred examples of the oligomer component include a dimer represented by the following general formula (2) and a trimer represented by the general formula (3).
前記共役ジエン系重合体と変性剤との反応は、前記変性剤を共役ジエン系重合体の活性末端と反応させることにより行う。 The reaction between the conjugated diene polymer and the modifying agent is performed by reacting the modifying agent with the active terminal of the conjugated diene polymer.
変性剤における低分子化合物とオリゴマー成分の比率はＧＰＣにより測定できる。
具体的には、低分子化合物からオリゴマー成分まで測定できるカラムを選択し、測定する。得られたピークにおいて、低分子化合物由来のピークの高分子側の最初の変極点から垂線を下ろし、低分子側成分の面積と高分子側成分の面積比を求める。この面積比が低分子化合物とオリゴマー成分の比率に相当する。
なお、オリゴマー成分の高分子側ピークは、標準ポリスチレン換算分子量から求めた該低分子化合物の分子量の１０倍以下の分子量となる点、あるいは該低分子化合物の分子量の１０倍以下の分子量となる点までに成分ピークが０となる場合は成分ピークが０となる点までを積算する。
The ratio of the low molecular weight compound and the oligomer component in the modifier can be measured by GPC.
Specifically, a column capable of measuring from a low molecular compound to an oligomer component is selected and measured. In the obtained peak, a perpendicular is drawn from the first inflection point on the polymer side of the peak derived from the low molecular compound, and the area ratio of the low molecular side component to the polymer side component is determined. This area ratio corresponds to the ratio between the low molecular weight compound and the oligomer component.
The polymer-side peak of the oligomer component has a molecular weight that is not more than 10 times the molecular weight of the low molecular weight compound determined from the standard polystyrene equivalent molecular weight, or a molecular weight that is not more than 10 times the molecular weight of the low molecular weight compound. If the component peak becomes 0 by then, the points up to the point where the component peak becomes 0 are integrated.
変性共役ジエン系重合体（Ａ−１）における、変性基を有する重合体の割合は、５質量％〜９０質量％が好ましく、２０質量％〜８０質量％がより好ましい。変性基を有する重合体の割合が、この範囲であると優れた性能が得られる。
なお、共役ジエン系重合体と変性剤との反応において、変性剤は共役ジエン系重合体の活性末端のモル数に対し、０．２倍モル〜１０倍モル用いることが好ましい。この範囲であると、優れた性能が得られるだけでなく、変性剤のコストも問題の無い程度である。
The proportion of the polymer having a modifying group in the modified conjugated diene polymer (A-1) is preferably 5% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass. When the proportion of the polymer having a modifying group is within this range, excellent performance can be obtained.
In the reaction between the conjugated diene polymer and the modifier, the modifier is preferably used in an amount of 0.2 to 10 moles relative to the number of moles of the active terminal of the conjugated diene polymer. Within this range, not only excellent performance can be obtained, but the cost of the modifier is not problematic.
次に、変性共役ジエン系重合体（Ａ−１）を構成する共役ジエン系重合体について説明する。
共役ジエン系重合体は、共役ジエン化合物と芳香族ビニル化合物を重合して得られるものである。
共役ジエン化合物としては、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、３−メチル−１，３−ペンタジエン、１，３−ヘプタジエン、１，３−ヘキサジエン等が挙げられる。これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。特に、１，３−ブタジエン、イソプレンが好ましい。
Next, the conjugated diene polymer constituting the modified conjugated diene polymer (A-1) will be described.
The conjugated diene polymer is obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1, 3-hexadiene etc. are mentioned. These may be used alone or in combination of two or more. In particular, 1,3-butadiene and isoprene are preferable.
芳香族ビニル化合物としては、スチレン、ｐ−メチルスチレン、α−メチルスチレン、ビニルエチルベンゼン、ビニルキシレン、ビニルナフタレン、ジフェニルエチレン等が挙げられる。これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。特にスチレンが好ましい。
また、共役ジエン系重合体のコールドフローを防止するために、分岐をコントロールするという観点から、ジビニルベンゼン等の多官能芳香族ビニル化合物も用いることができる。
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. These may be used alone or in combination of two or more. Styrene is particularly preferable.
In order to prevent cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene can also be used from the viewpoint of controlling branching.
前記共役ジエン系重合体は、芳香族ビニル化合物と共役ジエン化合物の重合体であるが、具体的には、ブタジエン−スチレン共重合体、イソプレン−スチレン共重合体、ブタジエン−イソプレン−スチレン共重合体が挙げられる。
共役ジエン系重合体を構成している共役ジエン化合物と芳香族ビニル化合物の質量比は、共役ジエン化合物／芳香族ビニル化合物が、８５／１５〜６５／３５であることが好ましく、８０／２０〜７０／３０であることがより好ましい。この範囲とすることにより、転がり抵抗とウェットスキッド抵抗のバランスに優れたゴム組成物を得ることができる。
The conjugated diene polymer is a polymer of an aromatic vinyl compound and a conjugated diene compound. Specifically, a butadiene-styrene copolymer, an isoprene-styrene copolymer, a butadiene-isoprene-styrene copolymer. Is mentioned.
The mass ratio of the conjugated diene compound and the aromatic vinyl compound constituting the conjugated diene polymer is preferably such that the conjugated diene compound / aromatic vinyl compound is 85/15 to 65/35, and 80/20 to More preferably, it is 70/30. By setting it as this range, the rubber composition excellent in the balance of rolling resistance and wet skid resistance can be obtained.
変性共役ジエン系重合体（Ａ−１）を構成する共役ジエン系重合体が、ブタジエン−スチレン共重合体、イソプレン−スチレン共重合体、ブタジエン−イソプレン−スチレン共重合体である場合、当該共役ジエン系重合体のガラス転移温度が、１つの場合はその温度が、複数ある場合は少なくともそのうちの１つの温度が、−５０℃〜−１０℃の範囲にあることが好ましく、−４５℃〜−１５℃の範囲にあることがさらに好ましい。
ウェットスキッド抵抗の改善を図る観点からは、上記共役ジエン系重合体のガラス転移温度は、−４５℃以上であることが好ましく、転がり抵抗を低減し、高い耐摩耗性を得る観点からは−１５℃以下であることが好ましい。
また、ガラス転移温度は、共役ジエン系重合体中のスチレン含量と共役ジエン化合物結合単位中に占めるビニル結合（１，２−結合と３，４−結合の合計）の割合を調節することにより制御できる。
なお、ガラス転移温度は、ＪＩＳ Ｋ７１２１−１９８７に記載されている方法により、加熱速度のみを毎分１０℃に変えてＤＳＣ曲線を求め、中間点ガラス転移温度（Ｔmg）を読み取る方法により求めることができる。
When the conjugated diene polymer constituting the modified conjugated diene polymer (A-1) is a butadiene-styrene copolymer, an isoprene-styrene copolymer, or a butadiene-isoprene-styrene copolymer, the conjugated diene In the case where the glass transition temperature of the system polymer is one, the temperature is preferably in the range of −50 ° C. to −10 ° C., and in the case where there are plural glass transition temperatures, the temperature is preferably −45 ° C. to −15 ° C. More preferably, it is in the range of ° C.
From the viewpoint of improving wet skid resistance, the glass transition temperature of the conjugated diene polymer is preferably −45 ° C. or more, and from the viewpoint of reducing rolling resistance and obtaining high wear resistance. It is preferable that it is below ℃.
The glass transition temperature is controlled by adjusting the styrene content in the conjugated diene polymer and the proportion of vinyl bonds (total of 1,2-bonds and 3,4-bonds) in the conjugated diene compound bond units. it can.
The glass transition temperature is determined by the method described in JIS K7121-1987, by changing the heating rate only to 10 ° C. per minute to obtain a DSC curve and reading the midpoint glass transition temperature (T mg ). Can do.
共役ジエン系重合体の共重合体鎖中における各単量体の組成分布については、分子鎖中において均一であってもよく、あるいは不均一であってもよい。分子鎖に沿って漸減・漸増する分布であってもよく、またブロックとして存在してもよい。ブロック構造としては、例えば、ブタジエンとスチレンからなる共重合体のブロックの場合に、ブタジエンとスチレンの比率が異なるブロックが繋がったもの等が挙げられる。 The composition distribution of each monomer in the copolymer chain of the conjugated diene polymer may be uniform or non-uniform in the molecular chain. The distribution may gradually decrease or increase along the molecular chain, or may exist as a block. As the block structure, for example, in the case of a block of a copolymer composed of butadiene and styrene, a block in which blocks having different ratios of butadiene and styrene are connected is exemplified.
本発明の好ましい実施形態の一つとして、共役ジエン系ランダム共重合体が挙げられる。例えば、共役ジエン系重合体が共役ジエンとスチレンから構成される場合、共役ジエン系重合体中のスチレンがランダムに共重合していることが好ましい。
ここで、ランダム共重合体とは、スチレンの連鎖長が３０以上の成分が下記のように少ないか、又は無いものをいう。
具体的には、Ｋｏｌｔｈｏｆｆの方法（Ｉ. Ｍ. ＫＯＬＴＨＯＦＦ, ｅｔ ａｌ., Ｊ. Ｐｏｌｙｍ. Ｓｃｉ．， １, ４２９（１９４６）に記載の方法）に従って、重合体を分解し、メタノールに不溶なポリスチレン量を測定する場合には、重合体量に対してメタノールに不溶なポリスチレン量が、１０質量％以下であることが好ましく、３質量％以下であることがより好ましい。
また、田中らの方法（Ｐｏｌｙｍｅｒ, ２２, １７２１（１９８１）に記載の方法）に従って、重合体をオゾン分解し、スチレン連鎖分布を分析する場合には、単離スチレン、すなわちスチレン単位の連鎖が１のスチレンが、全結合スチレンの４０質量％以上であり、かつ、長鎖ブロックスチレン、すなわちスチレン単位の連鎖が８以上のスチレンが、全結合スチレンの５質量％以下であることが好ましく、２．５質量％以下であることがさらに好ましい。
One preferred embodiment of the present invention is a conjugated diene random copolymer. For example, when the conjugated diene polymer is composed of conjugated diene and styrene, it is preferable that styrene in the conjugated diene polymer is randomly copolymerized.
Here, the random copolymer means a component having a styrene chain length of 30 or more as described below.
Specifically, the polymer is decomposed according to Kolthoff's method (method described in I. M. KOLTHOFF, et al., J. Polym. Sci., 1, 429 (1946)), and polystyrene insoluble in methanol is obtained. When measuring the amount, the amount of polystyrene insoluble in methanol with respect to the amount of polymer is preferably 10% by mass or less, more preferably 3% by mass or less.
Further, when the polymer is ozonolyzed according to the method of Tanaka et al. (Method described in Polymer, 22, 1721 (1981)) and the styrene chain distribution is analyzed, the isolated styrene, that is, the chain of styrene units is 1 It is preferable that the styrene is 40% by mass or more of the total bonded styrene and the long-chain block styrene, that is, the styrene having 8 or more chains of styrene units is 5% by mass or less of the total bonded styrene. More preferably, it is 5 mass% or less.
変性共役ジエン系重合体（Ａ−１）を構成する共役ジエン系重合体の重合反応としては、特開昭５９−１４０２１１号公報に記載されているように、共重合の途中に１，３−ブタジエンの一部を断続的に添加する方法で、芳香族ビニル化合物と共役ジエン化合物をランダムに共重合する方法が適用できる。
また、芳香族ビニル化合物を共役ジエン化合物とランダムに共重合する目的のランダム化剤として、あるいは共役ジエン化合物中のビニル結合量（１，２−結合と３，４−結合の合計量）を制御する目的のビニル化剤として、少量の極性化合物を添加するようにしてもよい。
極性化合物としては、例えば、テトラヒドロフラン、ジエチルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジメトキシベンゼン、２，２−ビス（２−オキソラニル）プロパン等のエーテル類；テトラメチルエチレンジアミン、ジピペリジノエタン、トリメチルアミン、トリエチルアミン、ピリジン、キヌクリジン等の第三級アミン化合物；カリウム−tert−アミラート、カリウム−tert−ブチラート、ナトリウム−tert−アミラート、ナトリウム−tert−ブチラート等のアルカリ金属アルコキシド化合物；トリフェニルホスフィン等のホスフィン化合物；アルキル又はアリールスルホン酸化合物等が挙げられる。
これらの極性化合物は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。
極性化合物の使用量は、目的と効果の程度に応じて選択される。通常、後述する開始剤１モルに対して０．０１倍モル〜１００倍モルが好ましい。
As a polymerization reaction of the conjugated diene polymer constituting the modified conjugated diene polymer (A-1), as described in JP-A No. 59-140221, 1,3- A method of randomly copolymerizing an aromatic vinyl compound and a conjugated diene compound by applying a part of butadiene intermittently is applicable.
Also, as a randomizing agent for the purpose of randomly copolymerizing aromatic vinyl compounds with conjugated diene compounds, or controlling the amount of vinyl bonds (total amount of 1,2-bonds and 3,4-bonds) in conjugated diene compounds A small amount of a polar compound may be added as a vinylating agent for the purpose.
Examples of the polar compound include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; alkalis such as potassium tert-amylate, potassium tert-butylate, sodium tert-amylate, sodium tert-butylate Metal alkoxide compounds; phosphine compounds such as triphenylphosphine; alkyl or aryl sulfonic acid compounds It is done.
These polar compounds may be used alone or in combination of two or more.
The amount of the polar compound used is selected according to the purpose and the degree of effect. Usually, 0.01 times mol-100 times mol are preferable with respect to 1 mol of initiators mentioned later.
変性共役ジエン系重合体（Ａ−１）を構成する共役ジエン系重合体中の共役ジエン部のビニル結合量（１，２−結合と３，４−結合の合計量）は、５０％〜７５％が好ましく、５５％〜７０％がさらに好ましい。ビニル結合量（１，２−結合と３，４−結合の合計量）がこの範囲であると、転がり抵抗が小さくかつウェットスキッド抵抗に優れ、また、優れた耐摩耗性が得られるようになる。 The vinyl bond amount (total amount of 1,2-bond and 3,4-bond) in the conjugated diene portion in the conjugated diene polymer constituting the modified conjugated diene polymer (A-1) is 50% to 75. % Is preferable, and 55% to 70% is more preferable. When the vinyl bond amount (total amount of 1,2-bond and 3,4-bond) is within this range, the rolling resistance is small, the wet skid resistance is excellent, and excellent wear resistance is obtained. .
上記共役ジエン系重合体の製造方法について説明する。共役ジエン系重合体は、炭化水素溶媒中、有機アルカリ金属化合物を開始剤として重合できる。炭化水素溶媒としては、飽和炭化水素または芳香族炭化水素が好ましい。
飽和炭化水素としては、ブタン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン等の脂環族炭化水素が挙げられる。芳香族炭化水素としては、ベンゼン、トルエン、キシレン等が挙げられる。
これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。
A method for producing the conjugated diene polymer will be described. The conjugated diene polymer can be polymerized in a hydrocarbon solvent using an organic alkali metal compound as an initiator. As the hydrocarbon solvent, a saturated hydrocarbon or an aromatic hydrocarbon is preferable.
Examples of the saturated hydrocarbon include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like.
These may be used alone or in combination of two or more.
有機アルカリ金属化合物よりなる開始剤としては、例えば、有機リチウム化合物、有機ナトリウム化合物、有機カリウム化合物等が挙げられるが、特に、有機リチウム化合物が好ましい。
有機リチウム化合物には、重合開始の能力がある全ての有機リチウム化合物が含まれる。例えば、低分子量のもの、可溶化したオリゴマーの有機リチウム化合物、また、１分子中に単独のリチウムを有するモノ有機リチウム化合物、１分子中に複数のリチウムを有する多官能性有機リチウム化合物等が挙げられる。
更に、有機基とリチウムの結合様式において、炭素−リチウム結合からなる化合物、窒素−リチウム結合からなる化合物、錫−リチウム結合からなる化合物等も挙げられる。
Examples of the initiator made of an organic alkali metal compound include an organic lithium compound, an organic sodium compound, an organic potassium compound, and the like, and an organic lithium compound is particularly preferable.
The organolithium compound includes all organolithium compounds capable of initiating polymerization. For example, low molecular weight, solubilized oligomeric organolithium compound, monoorganolithium compound having single lithium in one molecule, polyfunctional organolithium compound having plural lithium in one molecule, etc. It is done.
Further, examples of the bonding mode between the organic group and lithium include a compound composed of a carbon-lithium bond, a compound composed of a nitrogen-lithium bond, and a compound composed of a tin-lithium bond.
モノ有機リチウム化合物としては、例えば、ｎ−ブチルリチウム、sec−ブチルリチウム、tert−ブチルリチウム、ｎ−ヘキシルリチウム、ベンジルリチウム、フェニルリチウム、スチルベンリチウム等が挙げられる。
多官能性有機リチウム化合物としては、例えば、１，４−ジリチオブタン、sec−ブチルリチウムとジイソプロペニルベンゼンの反応物、１，３，５−トリリチオベンゼン、ｎ−ブチルリチウムと１，３−ブタジエンおよびジビニルベンゼンの反応物、ｎ−ブチルリチウムとポリアセチレン化合物の反応物等が挙げられる。
窒素−リチウム結合からなる化合物としては、例えば、リチウムジメチルアミド、リチウムジエチルアミド、リチウムジプロピルアミド、リチウムジ−ｎ−ヘキシルアミド、リチウムジイソプロピルアミド、リチウムヘキサメチレンイミド、リチウムピロリジド、リチウムピペリジド、リチウムヘプタメチレンイミド、リチウムモルホリド等が挙げられる。
これらの有機リチウム化合物は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。
有機リチウム化合物のなかで、ｎ−ブチルリチウム、sec−ブチルリチウムが特に好ましい。
Examples of the monoorganolithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenelithium and the like.
Examples of the polyfunctional organolithium compound include 1,4-dilithiobutane, a reaction product of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, n-butyllithium and 1,3-butadiene. And a reaction product of divinylbenzene, a reaction product of n-butyllithium and a polyacetylene compound, and the like.
Examples of the compound comprising a nitrogen-lithium bond include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, and lithium. Examples include heptamethylene imide and lithium morpholide.
These organolithium compounds may be used alone or in combination of two or more.
Of the organic lithium compounds, n-butyllithium and sec-butyllithium are particularly preferable.
上述した重合方法により得られる共役ジエン系重合体の活性末端と、上述した変性剤とを反応させることにより、変性共役ジエン系重合体（Ａ−１）の溶液が得られる。この溶液には、必要に応じて反応停止剤を添加することができる。
反応停止剤としては、通常、メタノール、エタノール、プロパノール等のアルコール類；ステアリン酸、ラウリン酸、オクタン酸等の有機酸；水等が使用される。
また、必要に応じて変性共役ジエン系重合体（Ａ−１）に含まれる金属類を脱灰することができる。脱灰は、通常、水、有機酸、無機酸、過酸化水素等の酸化剤等を重合体溶液に接触させて金属類を抽出し、その後水層を分離する方法で行われる。
A solution of the modified conjugated diene polymer (A-1) can be obtained by reacting the active terminal of the conjugated diene polymer obtained by the polymerization method described above with the above modifier. A reaction terminator can be added to this solution as needed.
As the reaction terminator, alcohols such as methanol, ethanol and propanol; organic acids such as stearic acid, lauric acid and octanoic acid; water and the like are usually used.
Moreover, the metals contained in the modified conjugated diene polymer (A-1) can be deashed as necessary. Deashing is usually performed by a method in which water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide or the like is brought into contact with the polymer solution to extract metals, and then the aqueous layer is separated.
変性共役ジエン系重合体（Ａ−１）は、標準ポリスチレン換算の重量平均分子量が１０万〜１００万であることが好ましい。この範囲の重量平均分子量であると、加工性と物性に関して良好なバランスが得られる。
また、変性共役ジエン系重合体（Ａ−１）の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比で表される分子量分布（Ｍｗ／Ｍｎ）は、１〜２が好ましく、１〜１．８がより好ましい。分子量分布（Ｍｗ／Ｍｎ）がこの範囲であると、転がり抵抗とウェットスキッド抵抗のバランスに優れ、かつ優れた剛性、耐摩耗性が得られる。
The modified conjugated diene polymer (A-1) preferably has a weight average molecular weight in terms of standard polystyrene of 100,000 to 1,000,000. When the weight average molecular weight is within this range, a good balance between processability and physical properties can be obtained.
Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified conjugated diene polymer (A-1) is preferably 1 to 2. -1.8 is more preferred. When the molecular weight distribution (Mw / Mn) is within this range, the balance between rolling resistance and wet skid resistance is excellent, and excellent rigidity and wear resistance are obtained.
変性共役ジエン系重合体（Ａ−１）の製造工程においては、回分式または、１個の反応器あるいは複数の連結された反応器を用いた連続式の重合方法を適用することが好ましい。
なお、変性共役ジエン系重合体（Ａ−１）は、該重合体に、伸展油を含まない。伸展油を含まない共役ジエン系重合体は、省燃費性を重視するタイヤ用途に好適に用いられる。
In the production process of the modified conjugated diene polymer (A-1), it is preferable to apply a batch polymerization method or a continuous polymerization method using one reactor or a plurality of connected reactors.
The modified conjugated diene polymer (A-1) does not contain an extending oil in the polymer. Conjugated diene polymers that do not contain an extender oil are suitably used for tire applications that emphasize fuel efficiency.
〔変性共役ジエン系重合体組成物の製造工程〕
上述のようにして得られた変性共役ジエン系重合体（Ａ−１）と、（Ａ−１）とは異なるゴム成分（Ａ−２）とを混合することにより、変性共役ジエン系重合体組成物が得られる。
[Production Process of Modified Conjugated Diene Polymer Composition]
A modified conjugated diene polymer composition obtained by mixing the modified conjugated diene polymer (A-1) obtained as described above and a rubber component (A-2) different from (A-1). Things are obtained.
ゴム成分（Ａ−２）としては、例えば、天然ゴム、ポリイソプレン、シス−１，４−ポリブタジエン、トランス−１，４−ポリブタジエン（ブタジエン結合単位部分の１，４−トランス結合量７０〜９５％）、乳化重合スチレン−ブタジエン共重合体、溶液重合スチレン−ブタジエンランダム共重合体（結合スチレン量５質量％〜５０質量％、ブタジエン結合単位部分のビニル結合量１０％〜８０％）、スチレン−（トランス−１，４−ブタジエン）共重合体（ブタジエン結合単位部分の１，４−トランス結合量７０〜９５％）、スチレン−イソプレン共重合体、ブタジエン−イソプレン共重合体、溶液重合スチレン−ブタジエン−イソプレンランダム共重合体、乳化重合スチレン−ブタジエン−イソプレンランダム共重合体、乳化重合スチレン−アクリロニトリル−ブタジエン共重合体、アクリロニトリル−ブタジエン共重合体、高ビニルスチレン−ブタジエン共重合体と低ビニルスチレン−ブタジエン共重合体のブロック共重合体、ポリスチレン−ポリブタジエン−ポリスチレンブロック共重合体等が挙げられる。
これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。
相容性の観点及び目的とする効果がより良く発揮されるための観点から、特に、天然ゴム、ポリイソプレン、シス−１，４−ポリブタジエンから選ばれるいずれか１種以上であることが好ましい。なお、シス−１，４−ポリブタジエンとは、ブタジエン結合単位部分の１，４−シス結合量が７０％以上の重合体であるものとする。
Examples of the rubber component (A-2) include natural rubber, polyisoprene, cis-1,4-polybutadiene, trans-1,4-polybutadiene (1,4-trans bond amount of butadiene bond unit portion 70 to 95%). ), Emulsion-polymerized styrene-butadiene copolymer, solution-polymerized styrene-butadiene random copolymer (bonded styrene content 5% to 50% by weight, vinyl bond content 10% to 80% in the butadiene bond unit portion), styrene- ( Trans-1,4-butadiene) copolymer (70-95% of 1,4-trans bonds in the butadiene bond unit portion), styrene-isoprene copolymer, butadiene-isoprene copolymer, solution-polymerized styrene-butadiene- Isoprene random copolymer, emulsion polymerization styrene-butadiene-isoprene random copolymer, emulsion polymerization steel -Acrylonitrile-butadiene copolymer, acrylonitrile-butadiene copolymer, block copolymer of high vinyl styrene-butadiene copolymer and low vinyl styrene-butadiene copolymer, polystyrene-polybutadiene-polystyrene block copolymer, etc. Can be mentioned.
These may be used alone or in combination of two or more.
From the viewpoint of better compatibility and the purpose of achieving the intended effect better, it is particularly preferable that it is at least one selected from natural rubber, polyisoprene, and cis-1,4-polybutadiene. The cis-1,4-polybutadiene is a polymer having a 1,4-cis bond amount of a butadiene bond unit portion of 70% or more.
変性共役ジエン系重合体（Ａ−１）と、ゴム成分（Ａ−２）との質量比は、１０／９０〜９０／１０が好ましく、２０／８０〜８０／２０がより好ましい。この範囲で混合することにより、転がり抵抗とウェットスキッド抵抗のバランスに優れ、かつ剛性、耐摩耗性にも優れた性能が発揮できる。 The mass ratio between the modified conjugated diene polymer (A-1) and the rubber component (A-2) is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. By mixing in this range, the balance between rolling resistance and wet skid resistance is excellent, and the performance with excellent rigidity and wear resistance can be exhibited.
変性共役ジエン系重合体組成物は、変性共役ジエン系重合体（Ａ−１）とゴム成分（Ａ−２）の合計１００質量部に対して、補強性充填剤１質量部〜２００質量部、加硫剤および加硫促進剤を合計０．１質量部〜３０質量部混合し、製造することが好ましい。
この配合比率とすることにより、補強性充填剤の分散性が良好になり、優れた加硫ゴムの性能が発揮されるようになる。
補強性充填剤は、本実施の形態の変性共役ジエン系重合体組成物を、タイヤ、防振ゴム等の自動車部品、靴等の用途に用いる場合には、シリカ系充填剤が好ましく、特に一次粒子径が５０ｎｍ以下の合成ケイ酸が好ましい。合成ケイ酸としては、湿式シリカ、乾式シリカが特に好ましい。
なお、補強性充填剤としてはカーボンブラックも用いることができる。例えば、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイト等が挙げられ、特にファーネスブラックが好ましい。
The modified conjugated diene polymer composition is composed of 1 part by mass to 200 parts by mass of a reinforcing filler with respect to 100 parts by mass in total of the modified conjugated diene polymer (A-1) and the rubber component (A-2). It is preferable to produce a vulcanizing agent and a vulcanization accelerator by mixing a total of 0.1 to 30 parts by mass.
By using this blending ratio, the dispersibility of the reinforcing filler is improved, and excellent vulcanized rubber performance is exhibited.
The reinforcing filler is preferably a silica-based filler when the modified conjugated diene polymer composition of the present embodiment is used for automobile parts such as tires and vibration-proof rubbers, shoes, etc. Synthetic silicic acid having a particle size of 50 nm or less is preferred. As the synthetic silicic acid, wet silica and dry silica are particularly preferable.
Carbon black can also be used as the reinforcing filler. For example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be mentioned, and furnace black is particularly preferable.
加硫剤としては、例えば粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄等の硫黄；一塩化硫黄、二塩化硫黄等のハロゲン化硫黄；ジクミルパーオキシド、ジ−tert−ブチルパーオキシド等の有機過酸化物等が挙げられる。これらの中でも硫黄が好ましく、粉末硫黄が特に好ましい。
加硫剤の配合割合は、変性共役ジエン系重合体組成物中のゴム成分である（Ａ−１）成分と（Ａ−２）成分の合計１００質量部に対して、０．１質量部〜１５質量部であるものとし、０．３質量部〜１０質量部が好ましく、０．５質量部〜５質量部がより好ましい。
Examples of the vulcanizing agent include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide and di-tert-butyl. Examples thereof include organic peroxides such as peroxides. Among these, sulfur is preferable, and powder sulfur is particularly preferable.
The blending ratio of the vulcanizing agent is 0.1 parts by mass to 100 parts by mass in total of the component (A-1) and the component (A-2) which are rubber components in the modified conjugated diene polymer composition. It shall be 15 mass parts, 0.3 mass part-10 mass parts are preferable, and 0.5 mass part-5 mass parts are more preferable.
加硫促進剤としては、例えば、スルフェンアミド系、チオウレア系、チアゾール系、ジチオカルバミン酸系、キサントゲン酸系加硫促進剤等が挙げられる。
加硫促進剤の配合割合は、変性共役ジエン系重合体組成物中のゴム成分である（Ａ−１）成分と（Ａ−２）成分の合計１００質量部に対して、０．１質量部〜１５質量部であるものとし、０．３質量部〜１０質量部が好ましく、０．５質量部〜５質量部がより好ましい。
ゴム配合剤としては、例えば、さらに加硫助剤、伸展油等を用いることができる。
加硫助剤としては、例えば、ステアリン酸や酸化亜鉛等が挙げられる。
Examples of the vulcanization accelerator include sulfenamide-based, thiourea-based, thiazole-based, dithiocarbamic acid-based, xanthogenic acid-based vulcanization accelerators, and the like.
The blending ratio of the vulcanization accelerator is 0.1 parts by mass with respect to a total of 100 parts by mass of the component (A-1) and the component (A-2) which are rubber components in the modified conjugated diene polymer composition. It shall be-15 mass parts, 0.3 mass part-10 mass parts are preferable, and 0.5 mass part-5 mass parts are more preferable.
As the rubber compounding agent, for example, a vulcanization aid, an extending oil, and the like can be used.
Examples of the vulcanization aid include stearic acid and zinc oxide.
伸展油としては、例えば、アロマ系、ナフテン系、パラフィン系、シリコーン系等の伸展油を、目的に応じて選択し使用する。
伸展油の使用量は、変性共役ジエン系重合体組成物中のゴム成分である（Ａ−１）成分と（Ａ−２）成分の合計１００質量部に対して、１質量部〜５０質量部が好ましい。具体的には、省燃費性を重視するタイヤ用途とするときには、１質量部〜３０質量部が好ましい。
伸展油の添加量を上記範囲とすることにより、配合物の加工性が優れ、かつ補強性充填剤の分散性が良好なものとなり、引張強度、耐摩耗性、耐熱性等のバランスが優れたものとなる。
As the extending oil, for example, an aroma-based, naphthenic-based, paraffin-based, or silicone-based extending oil is selected and used according to the purpose.
The amount of the extender oil used is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the components (A-1) and (A-2) which are rubber components in the modified conjugated diene polymer composition. Is preferred. Specifically, when the tire is used with an emphasis on fuel efficiency, the amount is preferably 1 part by mass to 30 parts by mass.
By making the addition amount of the extender oil within the above range, the processability of the composition is excellent and the dispersibility of the reinforcing filler is excellent, and the balance of tensile strength, wear resistance, heat resistance, etc. is excellent. It will be a thing.
また、その他のゴム配合剤としては、例えば、有機シランカップリング剤を使用することができる。
有機シランカップリング剤は、シリカ系充填剤とゴム成分とのカップリング、即ち相互結合作用を緊密にする機能を有した化合物である。すなわち、有機シランカップリング剤は、その分子内に、ゴム成分の二重結合及びシリカ系充填剤の表面に対して、それぞれ親和性または結合性を有する官能基を含有した化合物である。
有機シランカップリング剤の使用量は、上記シリカ系充填剤に対して、０．１質量％〜２０質量％が好ましく、０．１質量％〜１５質量％がより好ましい。
Moreover, as another rubber compounding agent, for example, an organic silane coupling agent can be used.
The organic silane coupling agent is a compound having a function of coupling a silica-based filler and a rubber component, that is, a mutual bonding action. That is, the organic silane coupling agent is a compound containing functional groups having affinity or binding property for the double bond of the rubber component and the surface of the silica filler in the molecule.
0.1 mass%-20 mass% are preferable with respect to the said silica type filler, and, as for the usage-amount of an organosilane coupling agent, 0.1 mass%-15 mass% are more preferable.
有機シランカップリング剤としては、例えば、ビス−[３−（トリエトキシシリル）−プロピル]−テトラスルフィド、ビス−[３−（トリエトキシシリル）−プロピル]−ジスルフィド、ビス−[２−（トリエトキシシリル）−エチル]−テトラスルフィド、３−メルカプトプロピル−トリメトキシシラン、３−トリエトキシシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、３−トリエトキシシリルプロピルベンゾチアゾールテトラスルフィド等が挙げられる。 Examples of the organic silane coupling agent include bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, and bis- [2- (tri Ethoxysilyl) -ethyl] -tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide and the like. .
本実施の形態における変性共役ジエン系重合体組成物には、上記成分のほか、常法に従って、炭酸カルシウム、クレー、タルク、マイカ、水酸化アルミニウム、水酸化マグネシウム等の充填剤、アミン系やフェノール系の老化防止剤、オゾン劣化防止剤、ジエチレングリコール等の活性剤、加工助剤、粘着付与剤、ワックス等のその他の配合剤を、目的に応じて必要量含有させることができる。 In the modified conjugated diene polymer composition in the present embodiment, in addition to the above components, fillers such as calcium carbonate, clay, talc, mica, aluminum hydroxide, magnesium hydroxide, amines and phenols are used according to conventional methods. System aging inhibitors, ozone degradation inhibitors, activators such as diethylene glycol, processing aids, tackifiers, and other compounding agents such as wax can be contained in necessary amounts depending on the purpose.
本実施の形態における変性共役ジエン系重合体組成物は、上記各成分を公知のゴム用混練機械、例えば、ロール、バンバリーミキサー等を用いて混合することにより製造できる。
なお、変性共役ジエン系重合体組成物は、必要に応じてシリカ系充填剤、カーボンブラック等の種々の添加剤を加えてマスターバッチとすることができる。マスターバッチとすることにより、加工性がよく、強度特性、耐摩耗性、転がり抵抗とウェットスキッド抵抗のバランスに優れた組成物となる。
The modified conjugated diene polymer composition in the present embodiment can be produced by mixing the above components using a known rubber kneading machine such as a roll or a Banbury mixer.
The modified conjugated diene polymer composition can be made into a master batch by adding various additives such as a silica filler and carbon black as necessary. By using a masterbatch, the composition is excellent in workability and has an excellent balance between strength characteristics, abrasion resistance, rolling resistance and wet skid resistance.
以下、本実施の形態における変性共役ジエン系重合体組成物について、具体的な実施例と比較例を挙げて説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the modified conjugated diene polymer composition in the present embodiment will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.
なお、製造例における試料の分析は下記に示す方法により行った。
（１）結合スチレン量
試料をクロロホルム溶液とし、スチレンのフェニル基によるＵＶ２５４ｎｍの吸収により結合スチレン量（質量％）を測定した（島津製作所製：ＵＶ−２４５０）。
（２）スチレン連鎖
Ｋｏｌｔｈｏｆｆの方法（Ｉ. Ｍ. ＫＯＬＴＨＯＦＦ, ｅｔ ａｌ., Ｊ. Ｐｏｌｙｍ. Ｓｃｉ．， １, ４２９（１９４６）に記載の方法）に従って重合体を分解し、メタノールに不溶なポリスチレン量を測定して、ブロックスチレン量（質量％）を求めた。
スチレン単位が１個のスチレン単連鎖、及びスチレン単位が８個以上連なったスチレン長連鎖の含有率は、田中らの方法（Ｐｏｌｙｍｅｒ, ２２, １７２１（１９８１）に記載）に従って、スチレン−ブタジエン共重合体をオゾンで分解した後、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって分析した。
（３）ブタジエン部分のミクロ構造
赤外分光光度計（日本分光製：ＦＴ−ＩＲ２３０）を使用して、６００〜１０００ｃｍ-1の範囲で赤外線スペクトルを測定した。試料を二硫化炭素溶液とし、溶液セルを用いた。その結果得られた吸光度よりハンプトンの方法の計算式に従い、ブタジエン部分のミクロ構造、すなわち、１，２−結合量（ビニル結合量）を求めた。
（４）ガラス転移温度
ＪＩＳ Ｋ７１２１−１９８７に記載の方法により、加熱速度のみを毎分１０℃に変えて測定した。ＤＳＣ曲線の中間点ガラス転移温度（Ｔmg）を読み取った。
（５）ムーニー粘度
ＪＩＳ Ｋ６３００−１：２００１に準拠して、１００℃で１分間予熱し、４分後の粘度を測定した。
（６）分子量
ポリスチレン系ゲルを充填剤としたカラム３本を連結して用いたＧＰＣを使用して、試料及び標準ポリスチレンのクロマトグラムを測定した（ガードカラム；東ソー ＴＳＫｇｕａｒｄｃｕｌｍｎ ＨＨＲ−Ｈ、カラム；東ソー ＴＳＫｇｅｌ Ｇ６０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ５０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ４０００ＨＨＲ）。
標準ポリスチレンの測定結果から検量線を作成し、これにより分子量及び分子量分布を計算した。溶離液にはテトラヒドロフラン（ＴＨＦ）を使用した。試料１０ｍｇを２０ｍＬのＴＨＦに溶解し、これを２００μＬカラムに注入して測定した。測定はオーブン温度４０℃、ＴＨＦの流量１．０ｍＬ／分の条件で、東ソー；ＨＬＣ８０２０（検出器；ＲＩ）を用いて行った。
（７）変性率
シリカ系ゲルを充填剤としたＧＰＣカラムに、変性した成分が吸着する特性を応用することにより測定した。
試料及び低分子量内部標準ポリスチレンを含む試料溶液に関して、上記（６）のポリスチレン系ゲルのＧＰＣ（東ソー；ＨＬＣ−８０２０）と、シリカ系カラム（ガードカラム；ＤＩＯＬ ４．６×１２．５ｍｍ ５ｍｉｃｒｏｎ、カラム；デュポン社 Ｚｏｒｂａｘ ＰＳＭ−１０００Ｓ、ＰＳＭ−３００Ｓ、ＰＳＭ−６０Ｓ）ＧＰＣ（東ソー；ＣＣＰ８０２０シリーズ、ビルドアップ型ＧＰＣシステム；ＡＳ−８０２０、ＳＤ−８０２２、ＣＣＰＳ、ＣＯ−８０２０、検出器；ＲＩ−８０２１、測定条件：オーブン温度；４０℃、ＴＨＦ流量；０．５ｍＬ／分）の両クロマトグラムを測定し、それらの差分よりシリカカラムへの吸着量を測定し変性率を求めた。
試料１０ｍｇおよび標準ポリスチレン５ｍｇを２０ｍＬのＴＨＦに溶解し、これを２００μＬカラムに注入して測定した。
具体的手順を下記に示す。
ポリスチレン系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料のピーク面積をＰ１、標準ポリスチレンのピーク面積をＰ２、シリカ系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料のピーク面積をＰ３、標準ポリスチレンのピーク面積をＰ４として、変性率（％）は［１−（Ｐ２×Ｐ３）／（Ｐ１×Ｐ４）］×１００で求めた（ここで、Ｐ１＋Ｐ２＝Ｐ３＋Ｐ４＝１００である）。
（８）変性剤の低分子化合物とオリゴマー成分の定量
カラム３本を連結して用いたＧＰＣ（東ソー；ＨＬＣ−８２２０、検出器；ＲＩ）を使用して試料及び標準ポリスチレンのクロマトグラムを測定した（カラム；東ソー ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ、ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ、ＴＳＫｇｅｌ Ｇ１０００ＨＸＬ）。
標準ポリスチレンの測定結果から検量線を作成し、これにより分子量の較正をした。溶離液にはテトラヒドロフラン（ＴＨＦ）を使用した。試料１．０ｍｇ／ｍＬのＴＨＦ溶液を２００μＬカラムに注入して測定した。測定はオーブン温度４０℃、ＴＨＦの流量１．０ｍＬ／分の条件で行った。
（９）オリゴマー成分の構造特定
試料をＴＨＦに溶解し、マトリックス（ジスラノール：１，８−ジヒドロキシ−９，１０−ジヒドロキシアントラセン−９−オン）と完全に混合させた。混合溶液をサンプルプレートに滴下し、溶媒蒸発後、ＭＡＬＤＩ−ＴＯＦ／ＭＳ測定を行った。
（測定条件）
装置：島津 ＡＸＩＭＡ ＣＦＲ plus
レーザー：窒素レーザー（３３７ｎｍ）
検出器形式：リニアモード
イオン検出：正イオン（ポジティブモード）
積算回数：５００回
マトリックス：ジスラノール １０ｍｇ／ｍＬ ＴＨＦ溶液
試料：１ｍｇ／ｍＬ ＴＨＦ溶液
スキャンレンジ：ｍ／ｚ１〜２０００
In addition, the analysis of the sample in a manufacture example was performed by the method shown below.
(1) Amount of bound styrene A sample was used as a chloroform solution, and the amount of bound styrene (mass%) was measured by absorption at UV254 nm by the phenyl group of styrene (manufactured by Shimadzu Corporation: UV-2450).
(2) Styrene chain Polymer is decomposed according to the method of Kolthoff (method described in I. M. KOLTHOFF, et al., J. Polym. Sci., 1, 429 (1946)), and the amount of polystyrene insoluble in methanol Was measured to determine the amount of block styrene (% by mass).
The content of styrene single chain with one styrene unit and styrene long chain with 8 or more styrene units connected is determined according to Tanaka et al. (Polymer, 22, 1721 (1981)). The coalescence was decomposed with ozone and then analyzed by gel permeation chromatography (GPC).
(3) Microstructure of butadiene portion Using an infrared spectrophotometer (manufactured by JASCO: FT-IR230), an infrared spectrum was measured in the range of 600 to 1000 cm- 1 . The sample was a carbon disulfide solution and a solution cell was used. From the resulting absorbance, the microstructure of the butadiene portion, that is, the 1,2-bond amount (vinyl bond amount) was determined according to the calculation formula of the Hampton method.
(4) Glass transition temperature The glass transition temperature was measured by changing the heating rate only to 10 ° C. per minute by the method described in JIS K7121-1987. The midpoint glass transition temperature (T mg ) of the DSC curve was read.
(5) Mooney Viscosity According to JIS K6300-1: 2001, preheating was performed at 100 ° C. for 1 minute, and the viscosity after 4 minutes was measured.
(6) Molecular weight The chromatogram of a sample and standard polystyrene was measured using GPC using three columns with a polystyrene gel as a filler (Guard column; Tosoh TSK guardcumn HHR-H, column; Tosoh). TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR).
A calibration curve was prepared from the measurement results of standard polystyrene, and molecular weight and molecular weight distribution were calculated thereby. Tetrahydrofuran (THF) was used as the eluent. 10 mg of a sample was dissolved in 20 mL of THF, and this was injected into a 200 μL column and measured. The measurement was performed using Tosoh; HLC8020 (detector; RI) under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
(7) Modification rate It measured by applying the characteristic which the modified | denatured component adsorb | sucks to the GPC column which used the silica type gel as the filler.
Regarding the sample solution containing the sample and the low molecular weight internal standard polystyrene, GPC (Tosoh; HLC-8020) of the above-mentioned polystyrene gel of (6) and a silica column (guard column; DIOL 4.6 × 12.5 mm 5 micron, column) DuPont Zorbax PSM-1000S, PSM-300S, PSM-60S) GPC (Tosoh; CCP8020 series, build-up GPC system; AS-8020, SD-8022, CCPS, CO-8020, detector; RI-8021, Both chromatograms of measurement conditions: oven temperature; 40 ° C., THF flow rate; 0.5 mL / min) were measured, and the amount of adsorption on the silica column was measured from the difference between them to determine the modification rate.
10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of THF, and this was injected into a 200 μL column and measured.
The specific procedure is shown below.
Sample with 100 as the total peak area of the chromatogram using the polystyrene column, P1 as the peak area of the sample, P2 as the peak area of the standard polystyrene, and 100 as the entire peak area of the chromatogram using the silica column Assuming that the peak area of P3 is P3 and the peak area of standard polystyrene is P4, the modification rate (%) was determined by [1- (P2 × P3) / (P1 × P4)] × 100 (where P1 + P2 = P3 + P4 = 100 Is).
(8) Quantification of low molecular weight compound and oligomer component of denaturant The chromatogram of the sample and standard polystyrene was measured using GPC (Tosoh; HLC-8220, detector; RI) used by connecting three columns. (Column; Tosoh TSKgel G3000HXL, TSKgel G2000HXL, TSKgel G1000HXL).
A calibration curve was created from the measurement results of standard polystyrene, and the molecular weight was calibrated. Tetrahydrofuran (THF) was used as the eluent. A sample 1.0 mg / mL THF solution was injected into a 200 μL column and measured. The measurement was performed under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
(9) Structure identification of oligomer component The sample was dissolved in THF and thoroughly mixed with a matrix (disranol: 1,8-dihydroxy-9,10-dihydroxyanthracen-9-one). The mixed solution was dropped on the sample plate, and after solvating the solvent, MALDI-TOF / MS measurement was performed.
(Measurement condition)
Equipment: Shimadzu AXIMA CFR plus
Laser: Nitrogen laser (337 nm)
Detector type: Linear mode Ion detection: Positive ion (positive mode)
Integration count: 500 times Matrix: Disranol 10 mg / mL THF solution Sample: 1 mg / mL THF solution Scan range: m / z 1 to 2000
〔変性共役ジエン系重合体（Ａ−１）製造例１〕
内容積１０Ｌ、撹拌機及びジャケットを具備し、温度制御が可能なオートクレーブを反応器として使用した。不純物を除去したブタジエン６２５ｇ、スチレン２２５ｇ、シクロヘキサン５５００ｇ、極性物質として２，２−ビス（２−オキソラニル）プロパン１．１２ｇを反応器へ入れ、反応器内温度を３０℃に保持した。重合開始剤としてｎ−ブチルリチウム８.７２ｍｍｏｌを含むシクロヘキサン溶液を反応器に供給した。反応開始後、重合による発熱で反応器内の温度上昇が確認された。前記重合開始剤添加後７分〜１２分に亘って、ブタジエン５０ｇを１０ｇ／分の速度で供給した。最終的な反応器内の温度は７７℃に達した。
重合反応終了後、反応器に、テトラグリシジル−１,３−ビスアミノメチルシクロヘキサン（単量体）８９．９質量％とオリゴマー成分１０．１質量％の混合物（変性剤Ｘ）を４．３６ｍｍｏｌを添加し、７５℃で５分間攪拌して変性反応を行った。
この重合体溶液に酸化防止剤（２，６−ジ−tert−ブチル−４−メチルフェノール；ＢＨＴ）を１．８ｇ添加後、変性共重合体溶液の溶媒を除去し、変性スチレン−ブタジエン共重合体（試料Ａ−１−１）を得た。
前記変性剤ＸのＧＰＣ曲線を図１に示す。また、測定に使用したＧＰＣの標準ポリスチレンによる較正曲線を図２に示す。変性剤ＸのＭＡＬＤＩ−ＴＯＦ／ＭＡＳスペクトルを図３に示す。変性剤Ｘのオリゴマー成分の主成分は、前述した一般式（２）および一般式（３）であって、Ｒが１，３−ビス（メチレン）−シクロヘキサンであった。
[Modified Conjugated Diene Polymer (A-1) Production Example 1]
An autoclave having an internal volume of 10 L, a stirrer and a jacket and capable of temperature control was used as a reactor. 625 g of butadiene from which impurities were removed, 225 g of styrene, 5500 g of cyclohexane, and 1.12 g of 2,2-bis (2-oxolanyl) propane as a polar substance were put into the reactor, and the temperature in the reactor was maintained at 30 ° C. A cyclohexane solution containing 8.72 mmol of n-butyllithium as a polymerization initiator was supplied to the reactor. After the start of the reaction, an increase in temperature in the reactor was confirmed due to heat generated by polymerization. 50 g of butadiene was supplied at a rate of 10 g / min for 7 to 12 minutes after the addition of the polymerization initiator. The final reactor temperature reached 77 ° C.
After completion of the polymerization reaction, 4.36 mmol of a mixture (modifier X) of 89.9% by mass of tetraglycidyl-1,3-bisaminomethylcyclohexane (monomer) and 10.1% by mass of the oligomer component was added to the reactor. The mixture was added and stirred at 75 ° C. for 5 minutes to carry out a denaturing reaction.
After adding 1.8 g of an antioxidant (2,6-di-tert-butyl-4-methylphenol; BHT) to this polymer solution, the solvent of the modified copolymer solution was removed, and the modified styrene-butadiene copolymer was removed. A coalescence (sample A-1-1) was obtained.
A GPC curve of the modifier X is shown in FIG. Moreover, the calibration curve by the standard polystyrene of GPC used for the measurement is shown in FIG. The MALDI-TOF / MAS spectrum of the modifier X is shown in FIG. The main component of the oligomer component of the modifier X was the general formula (2) and general formula (3) described above, and R was 1,3-bis (methylene) -cyclohexane.
（試料Ａ−１−１）は、結合スチレン量２５質量％、結合ブタジエン量７５質量％、ブタジエン中の１，２−結合量（ビニル結合量）６５％であった。
スチレン連鎖は、Ｋｏｒｔｈｏｆｆの方法によるブロックスチレン量が０質量％、オゾン分解によるスチレン単連鎖は４８質量％、スチレン単位が８個以上連なったスチレン長連鎖は１質量％であった。
ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が５８万であった。変性率は８３％であった。また、ムーニー粘度は７５であった。
(Sample A-1-1) had a bound styrene content of 25% by weight, a bound butadiene content of 75% by weight, and a 1,2-bond content (vinyl bond content) of 65% in butadiene.
In the styrene chain, the amount of block styrene by the Korthoff method was 0% by mass, the styrene single chain by ozonolysis was 48% by mass, and the styrene long chain comprising 8 or more styrene units was 1% by mass.
The weight average molecular weight (Mw) of the molecular weight in terms of polystyrene was 580,000. The modification rate was 83%. The Mooney viscosity was 75.
〔変性共役ジエン系重合体（Ａ−１）製造例２〕
ブタジエンの量を６７０ｇ、スチレンの量を１８０ｇ、２，２−ビス（２−オキソラニル）プロパンの量を０．６８ｇ、ｎ−ブチルリチウムの量を８．４４ｍｍｏｌ、変性剤Ｘの量を４．２２ｍｍｏｌに変更した。その他の条件は製造例１と同様として、変性反応を行い、変性スチレン−ブタジエン共重合体（試料Ａ−１−２）を得た。
（試料Ａ−１−２）は、結合スチレン量２０質量％、結合ブタジエン量８０質量％、ブタジエン中の１，２−結合量（ビニル結合量）５５％であった。ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が５５万であった。変性率は８４％であった。ムーニー粘度は７３であった。
[Modified Conjugated Diene Polymer (A-1) Production Example 2]
The amount of butadiene is 670 g, the amount of styrene is 180 g, the amount of 2,2-bis (2-oxolanyl) propane is 0.68 g, the amount of n-butyllithium is 8.44 mmol, and the amount of modifier X is 4.22 mmol. Changed to Other conditions were the same as in Production Example 1, and a modification reaction was performed to obtain a modified styrene-butadiene copolymer (Sample A-1-2).
(Sample A-1-2) had a bonded styrene content of 20% by mass, a bonded butadiene content of 80% by mass, and a 1,2-bond content (vinyl bond content) of 55% in butadiene. The weight average molecular weight (Mw) of the molecular weight in terms of polystyrene was 550,000. The modification rate was 84%. The Mooney viscosity was 73.
〔変性共役ジエン系重合体（Ａ−１）製造例３〕
ブタジエンの量を６７０ｇ、スチレンの量を１８０ｇ、２，２−ビス（２−オキソラニル）プロパンの量を１．０８ｇ、ｎ−ブチルリチウムの量を８．４４ｍｍｏｌ、変性剤Ｘの量を４．２２ｍｍｏｌに変更した。その他の条件は、製造例１と同様の方法で重合、変性反応を実施し、変性スチレン−ブタジエン共重合体（試料Ａ−１−３）を得た。
（試料Ａ−１−３）は、結合スチレン量２０質量％、結合ブタジエン量８０質量％、ブタジエン中の１，２−結合量（ビニル結合量）６４％であった。ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が５７万であった。変性率は７８％であった。ムーニー粘度は７４であった。
[Modified Conjugated Diene Polymer (A-1) Production Example 3]
The amount of butadiene is 670 g, the amount of styrene is 180 g, the amount of 2,2-bis (2-oxolanyl) propane is 1.08 g, the amount of n-butyllithium is 8.44 mmol, and the amount of modifier X is 4.22 mmol. Changed to For other conditions, polymerization and modification reaction were carried out in the same manner as in Production Example 1 to obtain a modified styrene-butadiene copolymer (Sample A-1-3).
(Sample A-1-3) had a bonded styrene content of 20% by mass, a bonded butadiene content of 80% by mass, and a 1,2-bond content (vinyl bond content) in butadiene of 64%. The weight average molecular weight (Mw) of the molecular weight in terms of polystyrene was 570,000. The modification rate was 78%. The Mooney viscosity was 74.
〔共役ジエン系重合体（Ａ−１）製造例４〕
前記変性剤Ｘに替えて四塩化ケイ素を１．９８ｍｍｏｌ用いた。また、ｎ−ブチルリチウムの量を７．９３ｍｍｏｌ、２，２−ビス（２−オキソラニル）プロパンの量を１．０２ｇにそれぞれ変更した。
その他の条件は、製造例１と同様として、重合、カップリング反応を実施し、スチレン−ブタジエン共重合体（試料Ａ−１−４）を得た。
（試料Ａ−１−４）は、結合スチレン量２５質量％、結合ブタジエン量７５質量％、ブタジエン中の１，２−結合量（ビニル結合量）６５％であった。ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が６２万であった。なお、四塩化ケイ素でカップリングした重合体（試料Ａ−１−４）は、ＧＰＣのシリカカラムに吸着される成分がなかった。ムーニー粘度は７８であった。
[Conjugated Diene Polymer (A-1) Production Example 4]
Instead of the modifier X, 1.98 mmol of silicon tetrachloride was used. The amount of n-butyllithium was changed to 7.93 mmol, and the amount of 2,2-bis (2-oxolanyl) propane was changed to 1.02 g.
Other conditions were the same as in Production Example 1, and polymerization and coupling reaction were performed to obtain a styrene-butadiene copolymer (Sample A-1-4).
(Sample A-1-4) had a bound styrene content of 25% by weight, a bound butadiene content of 75% by weight, and a 1,2-bond content (vinyl bond content) of 65% in butadiene. The weight average molecular weight (Mw) of the polystyrene equivalent molecular weight was 620,000. In addition, the polymer (sample A-1-4) coupled with silicon tetrachloride had no component adsorbed on the silica column of GPC. The Mooney viscosity was 78.
〔変性共役ジエン系重合体（Ａ−１）製造例５〕
ブタジエンの量を５１７ｇ、スチレンの量を３３３ｇ、２，２−ビス（２−オキソラニル）プロパンの量を０．６２ｇ、ｎ−ブチルリチウムの量を９．９０ｍｍｏｌ、変性剤Ｘの量を４．９５ｍｍｏｌに変更した。その他の条件は、製造例１と同様として、重合、変性反応を実施し、変性スチレン−ブタジエン共重合体（試料Ａ−１−５）を得た。
（試料Ａ−１−５）は、結合スチレン量３７質量％、結合ブタジエン量６３質量％、ブタジエン中の１，２−結合量（ビニル結合量）４０％であった。ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が５７万であった。変性率は７９％であった。ムーニー粘度は７０であった。
[Modified Conjugated Diene Polymer (A-1) Production Example 5]
The amount of butadiene was 517 g, the amount of styrene was 333 g, the amount of 2,2-bis (2-oxolanyl) propane was 0.62 g, the amount of n-butyllithium was 9.90 mmol, and the amount of modifier X was 4.95 mmol. Changed to Other conditions were the same as in Production Example 1, and polymerization and modification reaction were carried out to obtain a modified styrene-butadiene copolymer (Sample A-1-5).
(Sample A-1-5) had a bound styrene content of 37% by weight, a bound butadiene content of 63% by weight, and a 1,2-bond amount (vinyl bond amount) in butadiene of 40%. The weight average molecular weight (Mw) of the molecular weight in terms of polystyrene was 570,000. The modification rate was 79%. The Mooney viscosity was 70.
〔変性共役ジエン系重合体（Ａ−１）製造例６〕
変性剤として、前記変性剤Ｘに替えて、テトラグリシジル−１,３−ビスアミノメチルシクロヘキサン（単量体）９６．０質量％とオリゴマー成分４．０質量％の混合物（変性剤Ｙ）を用いた。その他の条件は、製造例１と同様として、重合、変性反応を実施し、変性スチレン−ブタジエン共重合体（試料Ａ−１−６）を得た。
（試料Ａ−１−６）は、結合スチレン量２５質量％、結合ブタジエン量７５質量％、ブタジエン中の１，２−結合量（ビニル結合量）６５％であった。ポリスチレン換算分子量は、重量平均分子量（Ｍｗ）が５７万であった。変性率は８２％であった。ムーニー粘度は７２であった。
[Modified Conjugated Diene Polymer (A-1) Production Example 6]
Instead of the modifier X, a mixture of tetraglycidyl-1,3-bisaminomethylcyclohexane (monomer) 96.0% by mass and oligomer component 4.0% by mass (modifier Y) is used as the modifier. It was. Other conditions were the same as in Production Example 1, and polymerization and modification reaction were carried out to obtain a modified styrene-butadiene copolymer (Sample A-1-6).
(Sample A-1-6) had a bound styrene content of 25% by weight, a bound butadiene content of 75% by weight, and a 1,2-bond content (vinyl bond content) of 65% in butadiene. The weight average molecular weight (Mw) of the molecular weight in terms of polystyrene was 570,000. The modification rate was 82%. The Mooney viscosity was 72.
上記のようにして製造した変性スチレン−ブタジエン共重合体（試料Ａ−１−１）〜（Ａ−１−６）の製造条件、及び分析結果を下記表１に示した。 The production conditions and analysis results of the modified styrene-butadiene copolymers (samples A-1-1) to (A-1-6) produced as described above are shown in Table 1 below.
上記表１の（試料Ａ−１−１）〜（試料Ａ−１−６）を（Ａ−１）成分とし、天然ゴム、ポリイソプレン、シス−１，４−ポリブタジエンを（Ａ−２）成分として、下記表２に示す配合量に従って、変性共役ジエン系重合体組成物のサンプルを作製した。
なお、下記表２中のゴム成分とは、（Ａ−１）成分と（Ａ−２）成分との合計である。（Ａ−１）成分と（Ａ−２）成分の質量比は表３、表４、表５に示す。
(Sample A-1-1) to (Sample A-1-6) in Table 1 are used as component (A-1), and natural rubber, polyisoprene and cis-1,4-polybutadiene are used as component (A-2). As follows, samples of modified conjugated diene polymer compositions were prepared according to the blending amounts shown in Table 2 below.
In addition, the rubber component in following Table 2 is the sum total of (A-1) component and (A-2) component. The mass ratio of the component (A-1) to the component (A-2) is shown in Table 3, Table 4, and Table 5.
サンプルを作製する混練りはＪＩＳ Ｋ６２９９：２００１に準拠して、下記の方法により行った。
温度制御装置を具備する密閉混練機（内容量０．３リットル）を使用し、第一段の混練では、充填率６５％、ローター回転数５０／５７ｒｐｍの条件とし、ゴム成分、充填剤（シリカおよびカーボンブラック）、有機シランカップリング剤、伸展油、亜鉛華、ステアリン酸を混練した。この際、密閉混練機の温度を制御して、１５５〜１６０℃の排出温度で組成物を得た。
第二段の混練として、第一段の混錬で得た組成物に老化防止剤を加え、シリカの分散を向上させるため再度混練した。この場合も、密閉混練機の温度制御により組成物の排出温度を１５５〜１６０℃に調整した。
第二段の混錬で得た組成物に、硫黄、加硫促進剤を加えて、７０℃に設定したオープンロールにて第三段の混練を行った。
第三段の混錬で得られた組成物を成型し、１６０℃で所定時間、加硫プレスにて加硫した。
The kneading for preparing the sample was performed according to JIS K6299: 2001 by the following method.
A closed kneading machine (with an internal volume of 0.3 liter) equipped with a temperature control device is used. In the first stage kneading, the conditions are a filling rate of 65% and a rotor rotational speed of 50/57 rpm. And carbon black), organosilane coupling agent, extender oil, zinc white, and stearic acid. At this time, the temperature of the closed kneader was controlled to obtain a composition at a discharge temperature of 155 to 160 ° C.
As the second stage kneading, an anti-aging agent was added to the composition obtained by the first stage kneading and kneaded again to improve the dispersion of silica. Also in this case, the discharge temperature of the composition was adjusted to 155 to 160 ° C. by controlling the temperature of the closed kneader.
Sulfur and a vulcanization accelerator were added to the composition obtained by the second stage kneading, and the third stage kneading was performed with an open roll set at 70 ° C.
The composition obtained by the third stage kneading was molded and vulcanized with a vulcanizing press at 160 ° C. for a predetermined time.
各物性の測定は以下の方法で実施した。 Each physical property was measured by the following method.
（１）配合物ムーニー粘度
ＪＩＳ Ｋ６３００−１：２００１に準拠して、１３０℃で１分間予熱し、４分後の粘度を測定した。
（２）バウンドラバー量
第２段混練終了後の組成物約０．２ｇを約１ｍｍ角状に裁断し、ハリスかご（１００メッシュ金網製）へ入れ、質量を測定した。その後トルエン中に２４時間浸せき後、乾燥、質量を測定し、非溶解成分の量から充填剤に結合したゴムの量を計算してバウンドラバー量とした。
（３）引張試験
ＪＩＳ Ｋ６２５１：２００４の引張試験法により試験片の切断時の引張強度および３００％伸張時の引張応力（３００％モジュラス）を測定した。
（４）粘弾性特性
レオメトリックス・サイエンティフィック社製のアレス粘弾性試験機を使用した。ねじりモードで周波数１０Ｈｚ、各測定温度（０℃および５０℃）でひずみを変化させてｔａｎδと弾性率（Ｇ’）を測定した。
ひずみ１％で低温（０℃）の時のｔａｎδの高いものほど、ウェットスキッド抵抗が優れ、ひずみ３％で高温（５０℃）の時のｔａｎδの低いものほど転がり抵抗が小さい。また、ひずみ３％、５０℃で測定したＧ’を剛性の指標とした。
（５）反発弾性
ＪＩＳ Ｋ６２５５−１９９６によるリュプケ式反発弾性試験法で５０℃での反発弾性を測定した。
（６）耐摩耗性
アクロン摩耗試験機を使用し、荷重６ポンド、３０００回転の摩耗量を測定した。指数が高いほど耐摩耗性が優れることを示す。
(1) Compound Mooney Viscosity According to JIS K6300-1: 2001, preheating was performed at 130 ° C. for 1 minute, and the viscosity after 4 minutes was measured.
(2) Bound rubber amount About 0.2 g of the composition after completion of the second stage kneading was cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the mass was measured. Then, after dipping in toluene for 24 hours, drying and mass were measured, and the amount of rubber bound to the filler was calculated from the amount of non-dissolved components to obtain the bound rubber amount.
(3) Tensile test Tensile strength at the time of cutting the test piece and tensile stress at 300% elongation (300% modulus) were measured by the tensile test method of JIS K6251: 2004.
(4) Viscoelastic properties An Ares viscoelasticity tester manufactured by Rheometrics Scientific was used. In the torsion mode, tan δ and elastic modulus (G ′) were measured by changing the strain at a frequency of 10 Hz and each measurement temperature (0 ° C. and 50 ° C.).
The higher the tan δ when the strain is 1% and the low temperature (0 ° C.), the better the wet skid resistance, and the lower the tan δ when the strain is 3% and the high temperature (50 ° C.), the smaller the rolling resistance. G ′ measured at 3% strain and 50 ° C. was used as an index of rigidity.
(5) Rebound resilience The rebound resilience at 50 ° C. was measured by the Lüpke-type rebound resilience test method according to JIS K6255-1996.
(6) Abrasion resistance Using an Akron abrasion tester, the amount of wear at a load of 6 pounds and 3000 revolutions was measured. The higher the index, the better the wear resistance.
〔実施例１〜６、比較例１、２〕
（Ａ−１）成分として（試料Ａ−１−１）〜（Ａ−１−５）、（Ａ−２）成分として天然ゴム、ポリイソプレン、シス−１，４−ポリブタジエンを用いた。（Ａ−１）成分と（Ａ−２）成分の質量比および上記（１）〜（６）の項目の物性測定結果を表３に示す。なお、耐摩耗性は比較例１を１００として相対的な指数で表した。
[Examples 1 to 6, Comparative Examples 1 and 2]
(Sample A-1-1) to (A-1-5) were used as the component (A-1), and natural rubber, polyisoprene, and cis-1,4-polybutadiene were used as the component (A-2). Table 3 shows the mass ratio of the component (A-1) to the component (A-2) and the physical property measurement results of the items (1) to (6). The abrasion resistance was expressed as a relative index with Comparative Example 1 being 100.
表３に示すように、実施例１〜６は、変性剤Ｘの替わりにカップリング剤を使用した共役ジエン系重合体（試料Ａ−１−４）を配合した比較例１と比べ、転がり抵抗とウェットスキッド抵抗のバランスが改良され、さらに剛性や耐摩耗性が良好であった。また、変性剤Ｘを使用したが、結合スチレン量およびブタジエン中の１，２−結合量（ビニル結合量）が本発明の範囲外である変性共役ジエン系重合体（試料Ａ―１−５）を配合した比較例２は比較例１と比べ、転がり抵抗とウェットスキッド抵抗のバランスが改良されるが、実施例１〜６には及ばなかった。 As shown in Table 3, Examples 1-6 are rolling resistance compared with the comparative example 1 which mix | blended the conjugated diene type polymer (sample A-1-4) which used the coupling agent instead of the modifier X. And wet skid resistance balance was improved, and the rigidity and wear resistance were also good. Moreover, although the modifier X was used, the modified conjugated diene polymer (sample A-1-5) in which the amount of bound styrene and the amount of 1,2-bond (vinyl bond) in butadiene are outside the scope of the present invention. Compared with Comparative Example 1, Comparative Example 2 containing No. 1 improved the balance between rolling resistance and wet skid resistance, but did not reach Examples 1-6.
〔実施例３、比較例３〕
（Ａ−１）成分として、（試料Ａ−１−１）、（試料Ａ−１−６）８０重量部を用い、（Ａ−２）成分として天然ゴム２０重量部を用いた。その他の成分は、上記表２に示した配合量に従い、前記混練方法で変性共役ジエン系重合体組成物のサンプルを作製した。
各サンプルの上記（１）〜（６）の項目の物性測定結果を下記表４に示す。
なお、耐摩耗性は、比較例３の値を１００として、相対的な指数で表した。
[Example 3, Comparative Example 3]
As the component (A-1), 80 parts by weight of (Sample A-1-1) and (Sample A-1-6) were used, and 20 parts by weight of natural rubber were used as the component (A-2). For other components, samples of the modified conjugated diene polymer composition were prepared by the kneading method according to the blending amounts shown in Table 2 above.
The physical property measurement results of the items (1) to (6) of each sample are shown in Table 4 below.
The abrasion resistance was expressed as a relative index with the value of Comparative Example 3 being 100.
表４に示すように、実施例３は変性剤中の低分子化合物とオリゴマー組成比が本発明範囲外である比較例３と比べ、転がり抵抗とウェットスキッド抵抗のバランスが改良され、剛性や耐摩耗性についても良好であった。 As shown in Table 4, Example 3 has an improved balance of rolling resistance and wet skid resistance compared to Comparative Example 3 in which the composition ratio of the low molecular weight compound and the oligomer in the modifier is out of the scope of the present invention, and the rigidity and resistance to resistance are improved. Abrasion was also good.
〔実施例１、７、８〕、〔比較例４、５〕
（Ａ−１）成分として（試料Ａ−１−１）、（Ａ−２）成分として天然ゴムを下記表５に示す質量比で用いた。その他の成分は、上記表２に示した配合量に従い、前記混練方法で変性共役ジエン系重合体組成物のサンプルを作製した。
各サンプルの上記（１）〜（６）の項目の物性測定結果を下記表５に示す。
なお、耐摩耗性は比較例４の値を１００として、相対的な指数で表した。
[Examples 1, 7, 8], [Comparative Examples 4, 5]
(Sample A-1-1) was used as the component (A-1), and natural rubber was used as the component (A-2) at a mass ratio shown in Table 5 below. For other components, samples of the modified conjugated diene polymer composition were prepared by the kneading method according to the blending amounts shown in Table 2 above.
The physical property measurement results of the items (1) to (6) of each sample are shown in Table 5 below.
The wear resistance was expressed as a relative index with the value of Comparative Example 4 being 100.
表５に示すように、実施例１、７、８は（Ａ−１）成分と（Ａ−２）成分の質量比が本発明の範囲外である比較例４、５と比べ転がり抵抗とウェットスキッド抵抗のバランスが改良されており、剛性や耐摩耗性についても良好であった。 As shown in Table 5, Examples 1, 7, and 8 have rolling resistance and wetness compared with Comparative Examples 4 and 5 in which the mass ratio of the component (A-1) to the component (A-2) is outside the scope of the present invention. The balance of skid resistance was improved and the rigidity and wear resistance were also good.
本発明の変性共役ジエン系重合体組成物は、転がり抵抗とウェットスキッド抵抗のバランスに優れており、かつ剛性や耐摩耗性といった物理的特性にも優れているので、タイヤ用途、靴用途のほか、各種自動車部品、工業用品等としての産業上の利用可能性を有する。 The modified conjugated diene polymer composition of the present invention has an excellent balance between rolling resistance and wet skid resistance, and also has excellent physical properties such as rigidity and wear resistance. In addition, it has industrial applicability as various automobile parts, industrial articles and the like.
Claims (3)
（Ａ）下記変性共役ジエン系重合体（Ａ−１）と、当該（Ａ−１）とは異なるゴム成分（Ａ−２）とからなる変性共役ジエン系重合体組成物であって、（Ａ−１）と（Ａ−２）との質量比が１０／９０〜９０／１０である変性共役ジエン系重合体組成物。
ここで、（Ａ−１）は、共役ジエン化合物と芳香族ビニル化合物とが重合した共役ジエン系重合体の活性末端が変性剤と結合しているものであり、下記（ａ）〜（ｃ）の条件を満たしている変性共役ジエン系重合体である。
（ａ）前記変性剤が、分子中にグリシジルアミノ基を含む低分子化合物７５〜９５質量 ％と、当該低分子化合物の２量体以上のオリゴマー２５〜５質量％とからなる変 性剤である。
（ｂ）前記共役ジエン系重合体中の、共役ジエン化合物／芳香族ビニル化合物の質量比 が８５／１５〜６５／３５である。
（ｃ）前記共役ジエン系重合体中の共役ジエン部の１，４−結合／１，２−結合または ３，４−結合の比率が、５０／５０〜２５／７５である。
（Ｂ）補強性充填剤（但し、前記（Ａ）１００質量部に対して、１〜２００質量部。）。 A modified conjugated diene polymer composition containing the following (A) and (B).
(A) A modified conjugated diene polymer composition comprising the following modified conjugated diene polymer (A-1) and a rubber component (A-2) different from (A-1), -1) and a modified conjugated diene polymer composition having a mass ratio of (A-2) of 10/90 to 90/10.
Here, (A-1) is one in which the active end of a conjugated diene polymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound is bonded to a modifier, and the following (a) to (c) It is a modified conjugated diene polymer that satisfies the above conditions.
(A) The modifier is a modifier composed of 75 to 95% by mass of a low molecular compound containing a glycidylamino group in the molecule and 25 to 5% by mass of an oligomer that is a dimer or higher of the low molecular compound. .
(B) The mass ratio of the conjugated diene compound / the aromatic vinyl compound in the conjugated diene polymer is 85/15 to 65/35.
(C) The ratio of 1,4-bond / 1,2-bond or 3,4-bond of the conjugated diene moiety in the conjugated diene polymer is 50/50 to 25/75.
(B) Reinforcing filler (however, 1 to 200 parts by mass with respect to 100 parts by mass of (A)).
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| WO2019017067A1 (en) | 2017-07-19 | 2019-01-24 | 住友ゴム工業株式会社 | Rubber composition for tread, and pneumatic tire |
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| EP3492277A1 (en) | 2017-11-30 | 2019-06-05 | Sumitomo Rubber Industries Ltd. | Rubber composition for tire |
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| JP2012172020A (en) * | 2011-02-18 | 2012-09-10 | Toyo Tire & Rubber Co Ltd | Rubber composition, method for producing the same and pneumatic tire |
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| EP2738014A2 (en) | 2012-11-28 | 2014-06-04 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
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| WO2014178232A1 (en) | 2013-04-30 | 2014-11-06 | 住友ゴム工業株式会社 | Tire rubber composition and pneumatic tire |
| WO2014178336A1 (en) | 2013-04-30 | 2014-11-06 | 住友ゴム工業株式会社 | Pneumatic tire |
| WO2015104955A1 (en) | 2014-01-07 | 2015-07-16 | 住友ゴム工業株式会社 | Pneumatic tire |
| EP2905305A1 (en) | 2014-01-08 | 2015-08-12 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
| EP2974884A1 (en) | 2014-07-14 | 2016-01-20 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
| KR102031528B1 (en) | 2015-09-01 | 2019-10-14 | 데쿠세리아루즈 가부시키가이샤 | Photocurable resin composition and method for manufacturing image display device |
| KR20180002761A (en) * | 2015-09-01 | 2018-01-08 | 데쿠세리아루즈 가부시키가이샤 | Photocurable resin composition and method for manufacturing image display device |
| JP2019501272A (en) * | 2016-11-14 | 2019-01-17 | エルジー・ケム・リミテッド | Modified conjugated diene polymer and process for producing the same |
| US10703827B2 (en) | 2016-11-14 | 2020-07-07 | Lg Chem, Ltd. | Modified conjugated diene-based polymer and method for preparing the same |
| WO2019017067A1 (en) | 2017-07-19 | 2019-01-24 | 住友ゴム工業株式会社 | Rubber composition for tread, and pneumatic tire |
| EP3461656A1 (en) | 2017-09-29 | 2019-04-03 | Sumitomo Rubber Industries, Ltd. | Tire |
| EP3492277A1 (en) | 2017-11-30 | 2019-06-05 | Sumitomo Rubber Industries Ltd. | Rubber composition for tire |
| EP3511179A1 (en) | 2018-01-11 | 2019-07-17 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire |
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